Uncoupling system and environment simulation cells for fast-scaling modeling of complex continuum embeddings.

Continuum solvation models are becoming increasingly relevant in condensed matter simulations, allowing to characterize materials interfaces in the presence of wet electrified environments at a reduced computational cost with respect to all atomistic simulations. However, some challenges with the implementation of these models in plane-wave simulation packages still persists, especially when the goal is to simulate complex and heterogeneous environments. Among these challenges is the computational cost associated with large heterogeneous environments, which in plane-wave simulations has a direct effect on the basis-set size and, as a result, on the cost of the electronic structure calculation. Moreover, the use of periodic simulation cells is not well-suited for modeling systems embedded in semi-infinite media, which is often the case in continuum solvation models. To address these challenges, we present the implementation of a double-cell formalism, in which the simulation cell used for the continuum environment is uncoupled from the one used for the electronic-structure simulation of the quantum-mechanical system. This allows for a larger simulation cell to be used for the environment, without significantly increasing computational time. In this work, we show how the double-cell formalism can be used as an effective periodic boundary conditions correction scheme for nonperiodic and partially periodic systems. The accuracy of the double-cell formalism is tested using representative examples with different dimensionalities, both in vacuum and in a homogeneous continuum dielectric environment. Fast convergence and good speedups are observed for all the simulation setups, provided the quantum-mechanical simulation cell is chosen to completely fit the electronic density of the system.

Advanced capabilities for materials modelling with Quantum ESPRESSO.

Quantum EXPRESSO is an integrated suite of open-source computer codes for quantum simulations of materials using state-of-the-art electronic-structure techniques, based on density-functional theory, density-functional perturbation theory, and many-body perturbation theory, within the plane-wave pseudopotential and projector-augmented-wave approaches. Quantum EXPRESSO owes its popularity to the wide variety of properties and processes it allows to simulate, to its performance on an increasingly broad array of hardware architectures, and to a community of researchers that rely on its capabilities as a core open-source development platform to implement their ideas. In this paper we describe recent extensions and improvements, covering new methodologies and property calculators, improved parallelization, code modularization, and extended interoperability both within the distribution and with external software.

A generalized Poisson and Poisson-Boltzmann solver for electrostatic environments.

The computational study of chemical reactions in complex, wet environments is critical for applications in many fields. It is often essential to study chemical reactions in the presence of applied electrochemical potentials, taking into account the non-trivial electrostatic screening coming from the solvent and the electrolytes. As a consequence, the electrostatic potential has to be found by solving the generalized Poisson and the Poisson-Boltzmann equations for neutral and ionic solutions, respectively. In the present work, solvers for both problems have been developed. A preconditioned conjugate gradient method has been implemented for the solution of the generalized Poisson equation and the linear regime of the Poisson-Boltzmann, allowing to solve iteratively the minimization problem with some ten iterations of the ordinary Poisson equation solver. In addition, a self-consistent procedure enables us to solve the non-linear Poisson-Boltzmann problem. Both solvers exhibit very high accuracy and parallel efficiency and allow for the treatment of periodic, free, and slab boundary conditions. The solver has been integrated into the BigDFT and Quantum-ESPRESSO electronic-structure packages and will be released as an independent program, suitable for integration in other codes.

Self-consistent continuum solvation (SCCS): the case of charged systems.

The recently developed self-consistent continuum solvation model (SCCS) [O. Andreussi, I. Dabo, and N. Marzari, J. Chem. Phys. 136, 064102 (2012)] is applied here to charged species in aqueous solutions. Describing ions in solution represents a great challenge because of the large electrostatic interactions between the solute and the solvent. The SCCS model is tested over 106 monocharged species, both cations and anions, and we demonstrate its flexibility, notwithstanding its much reduced set of parameters, to describe charged species in solution. Remarkably low mean absolute errors are obtained with values of 2.27 and 5.54 kcal/mol for cations and anions, respectively. These results are comparable or better than the state of the art to describe solvation of charged species in water. Finally, differences of behavior between cations and anions are discussed.